Methods for making foams using blowing agents comprising unsaturated fluorocarbons

ABSTRACT

Disclosed herein are blowing agents comprising fluorocarbons and/or hydrofluorocarbons useful in foamable compositions. Also disclosed are methods for forming a foam comprising the aforementioned blowing agents.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application is a divisional application of and claims prioritythrough co-pending application Ser. No. 11/591,349, now allowed. Thisapplication also claims the benefit of priority of U.S. ProvisionalApplication 60/732,771, filed Nov. 1, 2005, and incorporated herein byreference, and is further related to co-filed and jointly ownedapplication titled Blowing Agents for Forming Foam ComprisingUnsaturated Fluorocarbons, (Attorney Docket No. FL1184 US NA) andfurther related to co-filed and jointly owned application also titledBlowing Agents for Forming Foam Comprising Unsaturated Fluorocarbons(Attorney Docket No. FL1318 US NA), both of which are also incorporatedherein by reference.

FIELD OF THE INVENTION

The disclosure herein relates to blowing agent compositions comprisingunsaturated fluorocarbons and/or unsaturated hydrofluorocarbons. Thedisclosure herein further relates to the use of the blowing agentcompositions in the process for manufacturing plastic foams.

BACKGROUND OF THE INVENTION

Closed-cell polyisocyanate-based foams are widely used for insulationpurposes, for example, in building construction and in the manufactureof energy efficient electrical appliances. In the construction industry,polyurethane (polyisocyanurate) board stock is used in roofing andsiding for its insulation and load-carrying capabilities. Poured andsprayed polyurethane foams are widely used for a variety of applicationsincluding insulating roofs, insulating large structures such as storagetanks, insulating appliances such as refrigerators and freezers,insulating refrigerated trucks and railcars, etc.

All of these various types of polyurethane foams require blowing(expansion) agents for their manufacture. Insulating foams depend on theuse of halocarbon blowing agents, not only to foam the polymer, butprimarily for their low vapor thermal conductivity, a very importantcharacteristic for insulation value. Historically, polyurethane foamsused CFCs (chlorofluorocarbons, for example CFC-11,trichlorofluoromethane) and HCFCs (hydrochlorofluorocarbons, for exampleHCFC-141b, 1,1-dichloro-1-fluoroethane) as the primary blowing agent.However, due to the implication of chlorine-containing molecules such asthe CFCs and HCFCs in the destruction of stratospheric ozone, theproduction and use of CFCs and HCFCs has been restricted by the MontrealProtocol. More recently, hydrofluorocarbons (HFCs), which do notcontribute to the destruction of stratospheric ozone, have been employedas blowing agents for polyurethane foams. An example of an HFC employedin this application is HFC-245fa (1,1,1,3,3-pentafluoropropane).

A second type of insulating foam is thermoplastic foam, primarilypolystyrene foam. Polyolefin foams (polystyrene, polyethylene, andpolypropylene) are widely used in insulation and packaging applications.These thermoplastic foams were generally made with CFC-12(dichlorodifluoromethane) as the blowing agent. More recently HCFCs(HCFC-22, chlorodifluoromethane) or blends of HCFCs (HCFC-22/HCFC-142b)or HFCs (HFC-152a) have been employed as blowing agents for polystyrene.

A third important type of insulating foam is phenolic foam. These foams,which have very attractive flammability characteristics, were generallymade with CFC-11 (trichlorofluoromethane) and CFC-113(1,1,2-trichloro-1,2,2-trifluoroethane) blowing agents

In addition to closed-cell foams, open-cell foams are also of commercialinterest, for example in the production of fluid-absorbent articles.U.S. Pat. No. 6,703,431 (Dietzen, et. al.) describes open-cell foamsbased on thermoplastics polymers that are useful for fluid-absorbenthygiene articles such as wound contact materials. U.S. Pat. No.6,071,580 (Bland, et. al.) describes absorbent extruded thermoplasticfoams which can be employed in various absorbency applications.Open-cell foams have also found application in evacuated or vacuum paneltechnologies, for example in the production of evacuated insulationpanels as described in U.S. Pat. No. 5,977,271 (Malone). Using open-cellfoams in evacuated insulation panels, it has been possible to obtain Rvalues of 10 to 15 per inch of thickness depending upon the evacuationor vacuum level, polymer type, cell size, density, and open cell contentof the foam. These open-cell foams have traditionally been producedemploying CFCs, HCFCs, or more recently, HFCs as blowing agents.

Multimodal foams are also of commercial interest, and are described, forexample, in U.S. Pat. No. 6,787,580 (Chonde, et. al.) and U.S. Pat. No.5,332,761 (Paquet, et. al.). A multimodal foam is a foam having amultimodal cell size distribution, and such foams have particularutility in thermally insulating articles since they often have higherinsulating values (R-values) than analogous foams having a generallyuniform cell size distribution. These foams have been produced employingCFCs, HCFCs, and, more recently, HFCs as the blowing agent.

As discussed above, the production of various types of foamshistorically employed CFCs as the blowing agent. In general, the CFCsproduce foams exhibiting good thermal insulation, low flammability andexcellent dimensional stability. However, despite these advantages theCFCs have fallen into disfavor due to their implication in thedestruction of stratospheric ozone, as well as their implication incontributing to global warming.

HCFCs have been proposed as CFC substitutes, and are currently employedas foam blowing agents. However, the HCFCs have also been shown tocontribute to the depletion of stratospheric ozone, and as a resulttheir use has come under scrutiny, and the widespread use of HCFCs isscheduled for eventual phase out under the Montreal Protocol.

More recently HFCs have been proposed and employed as foam blowingagents. The HFCs do not contribute to the destruction of stratosphericozone, but are of concern due to their contribution to the “greenhouseeffect”, i.e., they contribute to global warming. As a result of theircontribution to global warming, the HFCs have come under scrutiny, andtheir widespread use may also be limited in the future.

Hydrocarbons have also been proposed as foam blowing agents. However,these compounds are flammable, and many are photochemically reactive,and as a result contribute to the production of ground level ozone(i.e., smog). Such compounds are typically referred to as volatileorganic compounds (VOCs), and are subject to environmental regulations.

There is need for producing foams that provide low flammability, goodthermal insulation and high dimensional stability by using a blowingagent that has substantially no ozone depletion potential (ODP) and noor very low global warming potential (GWP).

There is also need to provide a process for producing plastic foamsemploying a blowing agent which has significantly less photochemicalreactivity than the hydrocarbons, and hence does not contribute to theformation of ambient ozone and ground level smog.

SUMMARY OF THE INVENTION

One aspect is for a blowing agent comprising at least one fluorocarbonor hydrofluorocarbon selected from the group consisting of:

-   -   (ii) a hydrofluorocarbon having the formula E- or Z—R¹CH═CHR²,        wherein R¹ and R² are, independently, C₁ to C₆ perfluoroalkyl        groups; and    -   (ii) a fluorocarbon or hydrofluorocarbon selected from the group        consisting of CF₃CF═CHF, CF₃CH═CF₂, CHF₂CF═CF₂, CHF₂CH═CHF,        CF₃CF═CH₂, CF₃CH═CHF, CH₂FCF═CF₂, CHF₂CH═CF₂, CHF₂CF═CHF,        CHF₂CF═CH₂, CF₃CH═CH₂, CH₃CF═CF₂, CH₂FCH═CF₂, CH₂FCF═CHF,        CHF₂CH═CHF, CF₃CF═CFCF₃, CF₃CF₂CF═CF₂, CF₃CF═CHCF₃,        CF₃CF₂CF═CH₂, CF₃CH═CHCF₃, CF₃CF₂CH═CH₂, CF₂═CHCF₂CF₃,        CF₂═CFCHFCF₃, CF₂═CFCF₂CHF₂, CHF₂CH═CHCF₃, (CF₃)₂C═CHCF₃,        CF₃CF═CHCF₂CF₃, CF₃CH═CFCF₂CF₃, (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂,        CF₃(CF₂)₃CF═CF₂, CF₃CF₂CF═CFCF₂CF₃, (CF₃)₂C═C(CF₃)₂,        (CF₃)₂CFCF═CHCF₃, CF₂═CFCF₂CH₂F, CF₂═CFCHFCHF₂, CH₂═C(CF₃)₂,        CH_([[2]]3)CF₂CF═CF₂, CH₂FCF═CFCHF₂, CH₂FCF₂CF═CF₂,        CF₂═C(CF₃)(CH₃), CH₂═C(CHF₂)(CF₃), CH₂═CHCF₂CHF₂,        CF₂═C(CHF₂)(CH₃), CHF═C(CF₃)(CH₃), CH₂═C(CHF₂)₂, CF₃CF═CFCH₃,        CH₃CF═CHCF₃, CF₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CF₃, CF₂═CHCF₂CF₂CF₃,        CF₂═CFCF₂CF₂CHF₂, CHF₂CF═CFCF₂CF₃, CF₃CF═CFCF₂CHF₂,        CF₃CF═CFCHFCF₃, CHF═CFCF(CF₃)₂, CF₂═CFCH(CF₃)₂, CF₃CH═C(CF₃)₂,        CF₂═CHCF(CF₃)₂, CH₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CHF₂,        CH₂═C(CF₃)CF₂CF₃, CF₂═CHCH(CF₃)₂, CHF═CHCF(CF₃)₂,        CF₂═C(CF₃)CH₂CF₃, CH₂═CFCF₂CF₂CHF₂, CF₂═CHCF₂CH₂CF₃,        CF₃CF═C(CF₃)(CH₃), CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂,        CH₂FCH═C(CF₃)₂, CH₃CF═C(CF₃)₂, CH₂═CHCF₂CHFCF₃,        CH₂═C(CF₃)CH₂CF₃, (CF₃)₂C═CHC₂F₅, (CF₃)₂CFCF═CHCF₃,        CH₂═CHC(CF₃)₃, (CF₃)₂C═C(CH₃)(CF₃), CH₂═CFCF₂CH(CF₃)₂,        CF₃CF═C(CH₃)CF₂CF₃, CF₃CH═CHCH(CF₃)₂, CH₂═CHCF₂CF₂CF₂CHF₂,        (CF₃)₂C═CHCF₂CH₃, CH₂═C(CF₃)CH₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅,        CH₂═CHCH₂CF₂C₂F₅, CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂,        CF₃CF═CHCH(CF₃)(CH₃), (CF₃)₂C═CFC₂H5, cyclo-CF₂CF₂CF₂CH═CH—,        cyclo-CF₂CF₂CH═CH—, CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃,        cyclo-CF₂CF₂CF═CF—, cyclo-CF₂CF═CFCF₂CF₂—,        cyclo-CF₂CF═CFCF₂CF₂CF₂, CF₃CF₂CF₂CF₂CH═CH₂, CF₃CH═CHCF₂CF₃,        CF₃CF₂CH═CHCF₂CF₃, CF₃CH═CHCF₂CF₂CF₃, CF₃CF═CFC₂F₅,        CF₃CF═CFCF₂CF₂C₂F₅, CF₃CF₂CF═CFCF₂C₂F₅, CF₃CH═CFCF₂CF₂C₂F₅,        CF₃CF═CHCF₂CF₂C₂F₅, CF₃CF₂CH═CFCF₂C₂F₅, CF₃CF₂CF═CHCF₂C₂F₅,        C₂F₅CF₂CF═CHCH₃, C₂F₅CF═CHCH₃, (CF₃)₂C═CHCH₃, CF₃C(CH₃)═CHCF₃,        CHF═CFC₂F₅, CHF₂CF═CFCF₃, (CF₃)₂C═CHF, CH₂FCF═CFCF₃,        CHF═CHCF₂CF₃, CHF₂CH═CFCF₃, CHF═CFCHFCF₃, CF₃CH═CFCHF₂,        CHF═CFCF₂CHF₂, CHF₂CF═CFCHF₂, CH₂CF═CFCF₃, CH₂FCH═CFCF₃,        CH₂═CFCHFCF₃, CH₂═CFCF₂CHF₂, CF₃CH═CFCH₂F, CHF═CFCH₂CF₃,        CHF═CHCHFCF₃, CHF═CHCF₂CHF₂, CHF₂CF═CHCHF₂, CHF═CFCHFCHF₂,        CF₃CF═CHCH₃, CF₂═CHCF₂Br, CHF═CBrCHF₂, CHBr═CHCF₃, CF₃CBr═CFCF₃,        CH₂═CBrCF₂CF₃, CHBr═CHCF₂CF₃, CH₂═CHCF₂CF₂Br, CH₂═CHCBrFCF₃,        CH₃CBr═CHCF₃, CF₃CBr═CHCH₃, (CF₃)₂C═CHBr, CF₃CF═CBrCF₂CF₃,        E-CHF₂CBr═CFC₂F₅, Z—CHF₂CBr═CFC₂F₅, CF₂═CBrCHFC₂F₅,        (CF₃)₂CFCBr═CH₂, CHBr═CF(CF₂)₂CHF₂, CH₂═CBrCF₂C₂F₅,        CF₂═C(CH₂Br)CF₃, CH₂═C(CBrF₂)CF₃, (CF₃)₂CHCH═CHBr,        (CF₃)₂C═CHCH₂Br, CH₂═CHCF(CF₃)CBrF₂, CF₂═CHCF₂CH₂CBrF₂,        CFBr═CHCF₃, CFBr═CFCF₃, CF₃CF₂CF₂CBr═CH₂, and CF₃(CF₂)₃CBr═CH₂.

Another aspect is for a closed cell foam prepared by foaming a foamablecomposition in the presence of a blowing agent described above.

A further aspect is for a foamable composition comprising a polyol and ablowing agent described above.

Another aspect is for a foam premix composition comprising a polyol anda blowing agent described above.

Additionally, one aspect is for a method of forming a foam comprising:

-   -   (a) adding to a foamable composition a blowing agent described        above; and    -   (b) reacting the foamable composition under conditions effective        to form a foam.

A further aspect is for a method of forming a polyisocyanate-based foamcomprising reacting at least one organic polyisocyanate with at leastone active hydrogen-containing compound in the presence of a blowingagent described above. Another aspect is for a polyisocyanate foamproduced by said method.

Other objects and advantages will become apparent to those skilled inthe art upon reference to the detailed description that hereinafterfollows.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire content of all citedreferences in this disclosure. Applicants also incorporate by referencethe co-owned and concurrently filed applications entitled “SolventCompositions Comprising Unsaturated Fluorinated Hydrocarbons” (AttorneyDocket # FL 1181 US PRV, U.S. Application No. 60/732,771), “BlowingAgents for Forming Foam Comprising Unsaturated Fluorocarbons” (AttorneyDocket # FL 1184 US PRV, U.S. Application No. 60/732,090), “AerosolPropellants Comprising Unsaturated Fluorocarbons” (Attorney Docket # FL1185 US PRV, U.S. Application No. 60/732,791), and “CompositionsComprising Fluoroolefins and Uses Thereof” (Attorney docket # FL 1159,U.S. Application No. 60/732,581). Further, when an amount,concentration, or other value or parameter is given as either a range,preferred range, or a list of upper preferable values and lowerpreferable values, this is to be understood as specifically disclosingall ranges formed from any pair of any upper range limit or preferredvalue and any lower range limit or preferred value, regardless ofwhether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range. It is not intended that the scope of the invention be limitedto the specific values recited when defining a range.

One aspect provides blowing agents having the formula E- or Z—R¹CH═CHR²(Formula I), wherein R¹ and R² are, independently, C₁ to C₆perfluoroalkyl groups. Examples of R¹ and R² groups include, but are notlimited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃,CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅,CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, and C(CF₃)₂CF₂C₂F₅. Exemplary,non-limiting Formula I compounds are presented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonafluoro-4-(trifluoromethyl)hex-2-ene F14tECF₃CH═CHC(CF₃)₃1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23EC₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iEC₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tE CF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2- ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂ 1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sE C₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5- (trifluoromethyl)hept-3-ene F24tEC₂F₅CH═CHC(CF₃)₃1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3- ene F33EC₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3- ene F33iEC₂F₅CF₂CH═CH—CF(CF₃)₂ 1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene F16E CF₃CH═CH(CF₂)₅CF₃1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16sECF₃CH═CHCF(CF₃)—(CF₂)₂C₂F₅ 1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-ene F16tE CF₃CH═CHC(CF₃)₂—CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25EC₂F₅CH═CH(CF₂)₄CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iEC₂F₅CH═CH—CF₂CF₂CF(CF₃)₂ 1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-ene F25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5- bis(trifluoromethyl)hept-3-ene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂ 1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-ene F34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6- (trifluoromethyl)oct-4-eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene F3i4E (CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro- 2(trifluoromethyl)oct-3-eneF3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂ 1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene F3i4sE (CF₃)₂CFCH═CH—CF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5- bis(trifluoromethyl)hept-3-eneF3i4tE (CF₃)₂CFCH═CH—C(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3- ene F26EC₂F₅CH═CH(CF₂)₅CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec- 3-ene F26sEC₂F₅CH═CHCF(CF₃)—(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene F26tE C₂F₅CH═CHC(CF₃)₂—CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5- bis(trifluoromethyl)oct-3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec- 4-ene F35iEC₂F₅CF₂CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-ene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6- bis(trifluoromethyl)oct-4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-ene F3i5iE (CF₃)₂CFCH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)oct-3-eneF3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅ 1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene F44E CF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec- 5-ene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-ene F44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-ene F44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,- bis(trifluoromethyl)oct-3-eneF4i4iE (CF₃)₂CFCF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)oct-4-eneF4i4sE (CF₃)₂CFCF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6- bis(trifluoromethyl)oct-4-eneF4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃ 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-ene F4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6- bis(trifluoromethyl)oct-4-eneF4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃ 1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-ene F4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,6,6,6-hexafluoro-2,2,5,5- tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include those fabricated fromstainless steels, in particular of the austenitic type, and thewell-known high nickel alloys such as Monel® nickel-copper alloys,Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may be conducted in semi-batch mode in whichthe perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyliodide reactant by means of a suitable addition apparatus such as a pumpat the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide withsaid perfluoroalkyltrihydroolefin are preferably within the range ofabout 150° C. to 300° C., preferably from about 170° C. to about 250°C., and most preferably from about 180° C. to about 230° C.

Suitable contact times for the reaction of the perfluoroalkyl iodidewith the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distilled prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basicsubstance may take place in the liquid phase preferably in the presenceof a solvent capable of dissolving at least a portion of both reactants.Solvents suitable for the dehydroiodination step include one or morepolar organic solvents such as alcohols (e.g., methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol),nitriles (e.g., acetonitrile, propionitrile, butyronitrile,benzonitrile, or adiponitrile), dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choiceof solvent may depend on the boiling point of the product and the easeof separation of traces of the solvent from the product duringpurification. Typically, ethanol or isopropanol are good solvents forthe reaction.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction vessel may be fabricated from glass,ceramic, or metal and is preferably agitated with an impellor orstirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, ethylene dichloride, chloroform, carbontetrachloride, or perchloroethylene), or ether (e.g., diethyl ether,methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran,dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of aphase transfer catalyst. Suitable phase transfer catalysts includequaternary ammonium halides (e.g., tetrabutylammonium bromide,tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride,dodecyltrimethylammonium chloride, and tricaprylylmethylammoniumchloride), quaternary phosphonium halides (e.g.,triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride),and cyclic ether compounds known in the art as crown ethers (e.g.,18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to a solidor liquid basic substance.

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion.

The compound of formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

The compositions disclosed herein may comprise a single compound ofFormula I, for example, one of the compounds in Table 1, or may comprisea combination of compounds of Formula I.

In addition to the inventive compounds described above, compoundspresented in Table 2 can be used as blowing agents.

TABLE 2 Name Structure Chemical name HFC-1225s C₃HF₅ HFC-1225yeCF₃CF═CHF 1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFC-1234s C₃H₂F₄ HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1243s C₃H₃F₃ HFC-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFC-1243ye CHF₂CF═CHF1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318s C₄F₈ FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327s C₄HF₇ HFC-1327myCF₃CF═CHCF₃ 1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF1,3,3,3-tetrafluoro-2- (trifluoromethyl)-1-propene HFC-1327czCF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1- butene HFC-1327cyeCF₂═CFCHFCF₃ 1,1,2,3,4,4,4-heptafluoro-1- butene HFC-1327cycCF₂═CFCF₂CHF₂ 1,1,2,3,3,4,4-heptafluoro-1- butene HFC-1336s C₄H₂F₆HFC-1336yf CF₃CF₂CF═CH₂ 2,3,3,4,4,4-hexafluoro-1- butene HFC-1336zeCHF═CHCF₂CF₃ 1,3,3,4,4,4-hexafluoro-1- butene HFC-1336eye CHF═CFCHFCF₃1,2,3,4,4,4-hexafluoro-1- butene HFC-1336eyc CHF═CFCF₂CHF₂1,2,3,3,4,4-hexafluoro-1- butene HFC-1336pyy CHF₂CF═CFCHF₂1,1,2,3,4,4-hexafluoro-2- butene HFC-1336qy CH₂FCF═CFCF₃1,1,1,2,3,4-hexafluoro-2- butene HFC-1336pz CHF₂CH═CFCF₃1,1,1,2,4,4-hexafluoro-2- butene HFC-1336mzy CF₃CH═CFCHF₂1,1,1,3,4,4-hexafluoro-2- butene HFC-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1- butene HFC-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1- butene HFC-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2- (trifluoromethyl)-1-propene HFC-1345s C₄H₃F₅HFC-1345qz CH₂FCH═CFCF₃ 1,1,1,2,4-pentafluoro-2- butene HFC-1345mzyCF₃CH═CFCH₂F 1,1,1,3,4-pentafluoro-2- butene HFC-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1- butene HFC-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2- butene HFC-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2- butene HFC-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1- butene HFC-1345pyz CHF₂CF═CHCHF₂1,1,2,4,4-pentafluoro-2- butene HFC-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1- butene HFC-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2- butene HFC-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1- butene HFC-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2- methyl-1-propene HFC-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3- trifluoro-1-propene HFC-1354s C₄H₄F₄HFC-1354fzc CH₂═CHCF₂CHF₂ 3,3,4,4-tetrafluoro-1-butene HFC-1354ctpCF₂═C(CHF₂)(CH₃) 1,1,3,3-tetrafluoro-2-methyl- 1-propene HFC-1354etmCHF═C(CF₃)(CH₃) 1,3,3,3-tetrafluoro-2-methyl- 1-propene HFC-1354tfpCH₂═C(CHF₂)₂ 2-(difluoromethyl)-3,3- difluoro-1-propene HFC-1354myCF₃CF═CFCH₃ 1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10s C₅F₁₀ FC-141-10myyCF₃CF═CFCF₂CF₃ 1,1,1,2,3,4,4,5,5,5- decafluoro-2-pentene FC-141-10cyCF₂═CFCF₂CF₂CF₃ 1,1,2,3,3,4,4,5,5,5- decafluoro-1-pentene HFC-1429sC₅HF₉ HFC-1429mzt (CF₃)₂C═CHCF₃ 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene HFC-1429myz CF₃CF═CHCF₂CF₃1,1,1,2,4,4,5,5,5-nonafluoro- 2-pentene HFC-1429mzy CF₃CH═CFCF₂CF₃1,1,1,3,4,4,5,5,5-nonafluoro- 2-pentene HFC-1429eyc CHF═CFCF₂CF₂CF₃1,2,3,3,4,4,5,5,5-nonafluoro- 1-pentene HFC-1429czc CF₂═CHCF₂CF₂CF₃1,1,3,3,4,4,5,5,5-nonafluoro- 1-pentene HFC-1429cycc CF₂═CFCF₂CF₂CHF₂1,1,2,3,3,4,4,5,5-nonafluoro- 1-pentene HFC-1429pyy CHF₂CF═CFCF₂CF₃1,1,2,3,4,4,5,5,5-nonafluoro- 2-pentene HFC-1429myyc CF₃CF═CFCF₂CHF₂1,1,1,2,3,4,4,5,5-nonafluoro- 2-pentene HFC-1429myye CF₃CF═CFCHFCF₃1,1,1,2,3,4,5,5,5-nonafluoro- 2-pentene HFC-1429eyym CHF═CFCF(CF₃)₂1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-butene HFC-1429cyzmCF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl)-1-buteneHFC-1429mzt CF₃CH═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-3-(trifluoromethyl)-2-butene HFC-1429czym CF₂═CHCF(CF₃)₂1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-butene HFC-1438s C₅H₂F₈HFC-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1- penteneHFC-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1- penteneHFC-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1438czzm CF₂═CHCH(CF₃)₂1,1,4,4,4-pentafluoro-3- (trifluoromethyl)-1-butene HFC-1438ezymCHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3- (trifluoromethyl)-1-buteneHFC-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1447s C₅H₃F₇ HFC-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1- pentene HFC-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1- pentene HFC-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1- pentene HFC-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3- methyl-2-buteneHFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-3- (trifluoromethyl)-2-buteneHFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene HFC-1456s C₅H₄F₆ HFC-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4- trifluoro-2-butene HFC-1456szy CF₃CF₂CF═CHCH₃3,4,4,5,5,5-hexafluoro-2- pentene HFC-1456mstz CF₃C(CH₃)═CHCF₃1,1,1,4,4,4-hexafluoro-2- methyl-2-butene HFC-1456fzce CH₂═CHCF₂CHFCF₃3,3,4,5,5,5-hexafluoro-1- pentene HFC-1456ftmf CH₂═C(CF₃)CH₂CF₃4,4,4-trifluoro-2- (trifluoromethyl)-1-butene FC-151-12s C₆F₁₂FC-151-12c CF₃(CF₂)₃CF═CF₂ 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (or perfluoro-1-hexene) FC-151-12mcyCF₃CF₂CF═CFCF₂CF₃ 1,1,1,2,2,3,4,5,5,6,6,6- dodecafluoro-3-hexene (orperfluoro-3-hexene) FC-151-12mmtt (CF₃)₂C═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2,3- bis(trifluoromethyl)-2-butene FC-151-(CF₃)₂CFCF═CFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro- 12mmzz4-(trifluoromethyl)-2-pentene HFC-152-11s C₆HF₁₁ HFC-152- (CF₃)₂C═CHC₂F₅1,1,1,4,4,5,5,5-octafluoro-2- 11mmtz (trifluoromethyl)-2-penteneHFC-152- (CF₃)₂CFCF═CHCF₃ 1,1,1,3,4,5,5,5-octafluoro-4- 11mmyyz(trifluoromethyl)-2-pentene HFC-1549s C₆H₃F₉ PFBE CF₃CF₂CF₂CF₂CH═CH₂3,3,4,4,5,5,6,6,6-nonafluoro- (or HFC-1549fz) 1-hexene (orperfluorobutylethylene) HFC- CH₂═CHC(CF₃)₃ 4,4,4-trifluoro-3,3-1549fztmm bis(trifluoromethyl)-1-butene HFC- (CF₃)₂C═C(CH₃)(CF₃)1,1,1,4,4,4-hexafluoro-3- 1549mmtts methyl-2-(trifluoromethyl)-2- buteneHFC-1549fycz CH₂═CFCF₂CH(CF₃)₂ 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene HFC-1549myts CF₃CF═C(CH₃)CF₂CF₃1,1,1,2,4,4,5,5,5-nonafluoro- 3-methyl-2-pentene HFC-1549mzzzCF₃CH═CHCH(CF₃)₂ 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl)-2-penteneHFC-1558s C₆H₄F₈ HFC-1558szy CF₃CF₂CF₂CF═CHCH₃3,4,4,5,5,6,6,6-octafluoro-2- hexene HFC-1558fzccc CH₂═CHCF₂CF₂CF₂CHF₂3,3,4,4,5,5,6,6-octafluoro-2- hexene HFC- (CF₃)₂C═CHCF₂CH₃1,1,1,4,4-pentafluoro-2- 1558mmtzc (trifluoromethyl)-2-penteneHFC-1558ftmf CH₂═C(CF₃)CH₂C₂F₅ 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene HFC-1567s C₆H₅F₇ HFC-1567ftsCF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2- methyl-1-penteneHFC-1567szz CF₃CF₂CF₂CH═CHCH₃ 4,4,5,5,6,6,6-heptafluoro-2- hexeneHFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅ 4,4,5,5,6,6,6-heptafluoro-1- hexeneHFC-1567sfyy CF₃CF₂CF═CFC₂H₅ 1,1,1,2,2,3,4-heptafluoro-3- hexeneHFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂ 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene HFC- CF₃CF═CHCH(CF₃)(CH₃)1,1,1,2,5,5,5-heptafluoro-4- 1567myzzm methyl-2-pentene HFC-(CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2- 1567mmtyf(trifluoromethyl)-2-pentene FC-161-14s C₇F₁₄ FC-161-14myyCF₃CF═CFCF₂CF₂C₂F₅ 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene FC-161-14mcyy CF₃CF₂CF═CFCF₂C₂F₅1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene HFCs-162-13sC₇HF₁₃ HFC-162- CF₃CH═CFCF₂CF₂C₂F₅ 1,1,1,3,4,4,5,5,6,6,7,7,7- 13mzytridecafluoro-2-heptene HFC162-13myz CF₃CF═CHCF₂CF₂C₂F₅1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFC-162-CF₃CF₂CH═CFCF₂C₂F₅ 1,1,1,2,2,4,5,5,6,6,7,7,7- 13mczytridecafluoro-3-heptene HFC-162- CF₃CF₂CF═CHCF₂C₂F₅1,1,1,2,2,3,5,5,6,6,7,7,7- 13mcyz tridecafluoro-3-heptene CyclicCyclo[—CX═CY(CXY)_(n)—] fluoroolefins HFC-C1316cc cyclo-CF₂CF₂CF═CF—1,2,3,3,4,4- hexafluorocyclobutene HFC-C1334cc cyclo-CF₂CF₂CH═CH—3,3,4,4- tetrafluorocyclobutene HFC-C1436 cyclo- 3,3,4,4,5,5,-CF₂CF₂CF₂CH═CH— hexafluorocyclopentene HFC-C1418y cyclo-1,2,3,3,4,4,5,5- CF₂CF═CFCF₂CF₂— octafluorocyclopentene FC-C151-10ycyclo- 1,2,3,3,4,4,5,5,6,6- CF₂CF═CFCF₂CF₂CF₂— decafluorocyclohexene

The compounds listed in Table 2 are available commercially or may beprepared by processes known in the art.

In addition to the inventive compounds described above, thebromine-containing fluorocarbons or hydrofluorocarbons presented inTable 3 can be used as blowing agents.

TABLE 3 Structure Chemical Names CF₂═CHCF₂Br3-bromo-1,1,3,3-tetrafluoropropene CF₂═CFCBrH₂3-bromo-1,1,2-trifluoropropene CHF═CBrCF₃2-bromo-1,3,3,3-tetrafluoropropene CHF═CHCBrF₂3-bromo-1,3,3-trifluoropropene CHF═CBrCHF₂2-bromo-1,3,3-trifluoropropene CHBr═CFCF₃1-bromo-2,3,3,3-tetrafluoropropene CHBr═CHCF₃1-bromo-3,3,3-trifluoropropene CH₂═CBrCF₃ 2-bromo-3,3,3-trifluoropropeneCH₂═CFCBrF₂ 3-bromo-2,3,3-trifluoropropene CFBr═CHCF₃1-bromo-1,3,3,3-tetrafluoropropene CFBr═CFCF₃ 1-bromopentafluoropropeneCH₂═CBrCF₂CF₃ 2-bromo-3,3,4,4,4-pentafluoro-1-butene CHBr═CHCF₂CF₃1-bromo-3,3,4,4,4-pentafluoro-1-butene CH₂═CHCF₂CF₂Br4-bromo-3,3,4,4-tetrafluoro-1-butene CH₂═CHCBrFCF₃3-bromo-3,4,4,4-tetrafluoro-1-butene CF₃CBr═CFCF₃2-bromo-1,1,1,3,4,4,4-heptafluoro-2-butene CH₃CBr═CHCF₃2-bromo-4,4,4-trifluoro-2-butene CF₃CBr═CHCH₃2-bromo-1,1,1-trifluoro-2-butene (CF₃)₂C═CHBr1-bromo-3,3,3-trifluoro-2-(trifluoromethyl)- propene CF₃CF═CBrCF₂CF₃3-bromo-1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene E-CHF₂CBr═CFC₂F₅E-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene Z-CHF₂CBr═CFC₂F₅Z-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene CF₂═CBrCHFC₂F₅2-bromo-1,1,3,4,4,5,5,5-octafluoro-1-pentene CHBr═CF(CF₂)₂CHF₂1-bromo-2,3,3,4,4,5,5-heptafluoro-1-pentene CH₂═CBrCF₂C₂F₅2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene CF₂═CHCF₂CH₂CBrF₂5-bromo-1,1,3,3,5,5-hexafluoro-1-pentene (CF₃)₂CFCBr═CH₂2-bromo-3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-buteneCF₂═C(CH₂Br)CF₃ 2-(bromomethyl)-1,1,3,3,3-pentafluoropropeneCH₂═C(CBrF₂)CF₃ 2-(bromodifluoromethyl)-3,3,3-trifluoropropene(CF₃)₂CHCH═CHBr 1-bromo-4,4,4-trifluoro-3-(trifluoromethyl)-1- butene(CF₃)₂C═CHCH₂Br 4-bromo-1,1,1-trifluoro-2-(trifluoromethyl)-2- buteneCH₂═CHCF(CF₃)CBrF₂ 3-(bromodifluoromethyl)-3,4,4,4-tetrafluoro-1- buteneCF₃CF₂CF₂CBr═CH₂ 2-bromo-3,3,4,4,5,5,5-heptafluoro-1-penteneCF₃(CF₂)₃CBr═CH₂ 2-bromo-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene

The compounds listed in Table 3 are available commercially or may beprepared by processes known in the art.

1-Bromo-3,3,4,4,4-pentafluoro-1-butene may be prepared by a three stepsequence beginning with reaction of phosphorous tribromide with3,3,4,4,4-pentafluoro-1-butanol to give4-bromo-1,1,1,2,2-pentafluorobutane. Thermal bromination of4-bromo-1,1,1,2,2-pentafluorobutane at 350-400° C. gives4,4-dibromo-1,1,1,2,2-pentafluorobutane which may in turn be heated withpowdered potassium hydroxide to give the desired bromobutene.

2-Bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene may be preparedby addition of bromine to 3,4,4-tetrafluoro-3-(trifluoromethyl)-1-butenefollowed by treatment of the resulting dibromide with ethanolicpotassium hydroxide.

Many of the compounds of Formula I, Table 1, Table 2 and Table 3 existas different configurational isomers or stereoisomers. When the specificisomer is not designated, the present disclosure is intended to includeall single configurational isomers, single stereoisomers, or anycombination thereof. For instance, CF₃CH═CHCF₃ is meant to represent theE-isomer, Z-isomer, or any combination or mixture of both isomers in anyratio. Another example is C₂F₅CF₂CH═CH—CF₂C₂F₅, by which is representedthe E-isomer, Z-isomer, or any combination or mixture of both isomers inany ratio.

HFC-1225ye may exist as one of two configurational isomers, E or Z.HFC-1225ye as used herein refers to the isomers, E-HFC-1225ye (CAS regno. 5595-10-8) or Z—HFC-1225ye (CAS reg. no. 5528-43-8), as well as anycombinations or mixtures of such isomers.

Blowing agents can comprise a single compound as listed, for example, inTable 2, or may comprise a combination of compounds from Table 2 or,alternatively, a combination of compounds from Table 1, Table 2, Table3, and/or Formula I.

The amount of the fluorocarbons (FCs) or HFCs contained in the presentcompositions (from, e.g., Formula I, Table 1, or Table 2, or Table 3)can vary widely, depending the particular application, and compositionscontaining more than trace amounts and less than 100% of the compoundare within broad the scope of the present disclosure.

The compositions disclosed herein may be prepared by any convenientmethod to combine the desired amounts of the individual components. Apreferred method is to weigh the desired component amounts andthereafter combine the components in an appropriate vessel. Agitationmay be used, if desired.

Other embodiments provide foamable compositions, and preferablythermoset or thermoplastic foam compositions, prepared using thecompositions of the present disclosure. In such foam embodiments, one ormore of the present compositions are included as or part of a blowingagent in a foamable composition, which composition preferably includesone or more additional components capable of reacting and/or foamingunder the proper conditions to form a foam or cellular structure.Another aspect relates to foam, and preferably closed cell foam,prepared from a polymer foam formulation containing a blowing agentcomprising the compositions of the present disclosure.

The present disclosure further relates to a method for replacing orsubstituting for the blowing agent in a foamable composition having aGWP of about 150 or more, or a high GWP blowing agent, with acomposition having a lower GWP. One method comprises providing acomposition comprising at least one fluoroolefin of the presentinvention as the replacement. In another embodiment of the presentinvention the foamable composition of the present invention, having alower GWP than the composition being replaced or substituted is used toproduce thermoplastic or thermoset foams. Global warming potentials(GWPs) are an index for estimating relative global warming contributiondue to atmospheric emission of a kilogram of a particular greenhouse gascompared to emission of a kilogram of carbon dioxide. GWP can becalculated for different time horizons showing the effect of atmosphericlifetime for a given gas. The GWP for the 100 year time horizon iscommonly the value referenced.

A high GWP blowing agent would be any compound capable of functioning asa blowing agent having a GWP at the 100 year time horizon of about 1000or greater, alternatively 500 or greater, 150 or greater, 100 orgreater, or 50 or greater. Foam expansion agents that are in need ofreplacement, based upon GWP calculations published by theIntergovernmental Panel on Climate Change (IPCC), include but are notlimited to HFC-134a and HFC-227ea.

The present disclosure will provide compositions that have zero or lowozone depletion potential and low global warming potential (GWP). Thefluoroolefins of the present invention or mixtures of fluoroolefins ofthis invention with other blowing agents or foamable compositions willhave global warming potentials that are less than many hydrofluorocarbonblowing agents or foamable compositions currently in use. Typically, thefluoroolefins of the present invention are expected to have GWP of lessthan about 25. One aspect of the present invention is to provide ablowing agent with a global warming potential of less than 1000, lessthan 500, less than 150, less than 100, or less than 50. Another aspectof the present invention is to reduce the net GWP of foamablecompositions by adding fluoroolefins to said mixtures.

The present invention further relates to a method for lowering the GWPof the methods for manufacturing open, closed and multi-modal foams,said method comprising combining at least one fluoroolefin of thepresent invention with a resin (for thermoplastic foams) or into aB-side mixture (thermoplastic) to produce a foamable composition with aGWP of lower than 25. The GWP of may be determined that the GWP of amixture or combination of compounds may be calculated as a weightedaverage of the GWP for each of the pure compounds.

The present compositions also preferably have an Ozone DepletionPotential (ODP) of not greater than 0.05, more preferably not greaterthan 0.02 and even more preferably about zero. As used herein, “ODP” isas defined in “The Scientific Assessment of Ozone Depletion, 2002, Areport of the World Meteorological Association's Global Ozone Researchand Monitoring Project,” which is incorporated herein by reference.

Certain embodiments provide foam premixes, foamable compositions, andpreferably polyurethane or polyisocyanate foam compositions, and methodsof preparing foams. In such foam embodiments, one or more of thecompositions of the present disclosure are included as a blowing agentin a foamable composition, which foamable composition preferablyincludes one or more additional components capable of reacting and/orfoaming under the proper conditions to form a foam or cellularstructure. Any of the methods well known in the art, such as thosedescribed in “Polyurethanes Chemistry and Technology,” Volumes I and II,Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y., which isincorporated herein by reference, may be used or adapted for use inaccordance with the foam embodiments.

In certain embodiments, it is often desirable to employ certain otheringredients in preparing foams. Among these additional ingredients arecatalysts, surfactants, flame retardants, preservatives, colorants,antioxidants, reinforcing agents, filler, antistatic agents, nucleatingagents and the like.

Polyurethane foams are generally prepared by combining and reacting anisocyanate with a polyol in the presence of a blowing or expanding agentand auxiliary chemicals added to control and modify both thepolyurethane reaction itself and the properties of the final polymer.For processing convenience, these materials can be premixed into twonon-reacting parts typically referred to as the “A-side” and the“B-side”.

The term “B-side” is intended to mean polyol or polyol containingmixture. A polyol containing mixture usually includes the polyol, theblowing or expanding agent and auxiliary chemicals, like catalysts,surfactants, stabilizers, chain extenders, cross-linkers, water, fireretardants, smoke suppressants, pigments, coloring materials, fillers,etc.

The term “A-side” is intended to mean isocyanate or isocyanatecontaining mixture. An isocyanate containing mixture may include theisocyanate, the blowing or expanding agent and auxiliary chemicals, likecatalysts, surfactants, stabilizers, chain extenders, cross-linkers,water, fire retardants, smoke suppressants, pigments, coloringmaterials, fillers, etc.

To prepare the foam, appropriate amounts of A-side and B-side are thencombined to react.

When preparing a foam by a process disclosed herein, it is generallypreferred to employ a minor amount of a surfactant to stabilize thefoaming reaction mixture until it cures. Such surfactants may comprise aliquid or solid organosilicone compound. Other, less preferredsurfactants include polyethylene glycol ethers of long chain alcohols,tertiary amine or alkanolamine salts of long chain alkyl acid sulfateesters, alkyl sulfonic esters and alkyl arylsulfonic acids. Thesurfactants are employed in amounts sufficient to stabilize the foamingreaction mixture against collapse and to prevent the formation of large,uneven cells. About 0.2 to about 5 parts or even more of the surfactantper 100 parts by weight of polyol are usually sufficient.

One or more catalysts for the reaction of the polyol with thepolyisocyanate may also be used. Any suitable urethane catalyst may beused, including tertiary amine compounds and organometallic compounds.Such catalysts are used in an amount which measurably increases the rateof reaction of the polyisocyanate. Typical amounts are about 0.1 toabout 5 parts of catalyst per 100 parts by weight of polyol.

Useful flame retardants include, for example,tri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate,tri(2,3-dibromopropyl)-phosphate, tri(1,3-dichloropropyl) phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminum trihydrate, polyvinyl chloride, and the like.

The methods of forming a foam generally comprise providing a blowingagent composition of the present disclosure, adding (directly orindirectly) the blowing agent composition to a foamable composition, andreacting the foamable composition under the conditions effective to forma foam or cellular structure. Any of the methods well known in the art,such as those described in “Polyurethanes Chemistry and Technology,”Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, NewYork, N.Y., which is incorporated herein by reference, may be used oradapted for use in accordance with the foam embodiments.

Polyisocyanate-based foams are prepared, e.g., by reacting at least oneorganic polyisocyanate with at least one active hydrogen-containingcompound in the presence of the blowing agent composition describedherein-above.

An isocyanate reactive composition can be prepared by blending at leastone active hydrogen-containing compound with the blowing agentcomposition. Advantageously, the blend contains at least 1 and up to 50,preferably up to 25 weight percent of the blowing agent composition,based on the total weight of active hydrogen-containing compound andblowing agent composition.

Active hydrogen-containing compounds include those materials having twoor more groups which contain an active hydrogen atom which reacts withan isocyanate. Preferred among such compounds are materials having atleast two hydroxyl, primary or secondary amine, carboxylic acid, orthiol groups per molecule. Polyols, i.e., compounds having at least twohydroxyl groups per molecule, are especially preferred due to theirdesirable reactivity with polyisocyanates.

Additional examples of suitable active hydrogen containing compounds canbe found in U.S. Pat. No. 6,590,005, incorporated herein by reference.For example, suitable polyester polyols include those prepared byreacting a carboxylic acid and/or a derivative thereof or apolycarboxylic anhydride with a polyhydric alcohol. The polycarboxylicacids may be any of the known aliphatic, cycloaliphatic, aromatic,and/or heterocyclic polycarboxylic acids and may be substituted, (e.g.,with halogen atoms) and/or unsaturated. Examples of suitablepolycarboxylic acids and anhydrides include oxalic acid, malonic acid,glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid,azelaic acid, sebacic acid, phthalic acid, isophthalic acid,terephthalic acid, trimellitic acid, trimellitic acid anhydride,pyromellitic dianhydride, phthalic acid anhydride, tetrahydrophthalicacid anhydride, hexahydrophthalic acid anhydride, endomethylenetetrahydrophthalic acid anhydride, glutaric acid anhydride acid, maleicacid, maleic acid anhydride, fumaric acid, and dimeric and trimericfatty acids, such as those of oleic acid which may be in admixture withmonomeric fatty acids. Simple esters of polycarboxylic acids may also beused such as terephthalic acid dimethylester, terephthalic acidbisglycol and extracts thereof. The polyhydric alcohols suitable for thepreparation of polyester polyols may be aliphatic, cycloaliphatic,aromatic, and/or heterocyclic. The polyhydric alcohols optionally mayinclude substituents which are inert in the reaction, for example,chlorine and bromine substituents, and/or may be unsaturated. Suitableamino alcohols, such as monoethanolamine, diethanolamine or the like mayalso be used. Examples of suitable polyhydric alcohols include ethyleneglycol, propylene glycol, polyoxyalkylene glycols (such as diethyleneglycol, polyethylene glycol, dipropylene glycol and polypropyleneglycol), glycerol and trimethylolpropane.

Suitable additional isocyanate-reactive materials include polyetherpolyols, polyester polyols, polyhydroxy-terminated acetal resins,hydroxyl-terminated amines and polyamines, and the like. Theseadditional isocyanate-reactive materials include hydrogen terminatedpolythioethers, polyamides, polyester amides, polycarbonates,polyacetals, polyolefins, polysiloxanes, and polymer polyols.

Other polyols include alkylene oxide derivatives of Mannich condensates,and aminoalkylpiperazine-initiated polyethers as described in U.S. Pat.Nos. 4,704,410 and 4,704,411. The low hydroxyl number, high equivalentweight alkylene oxide adducts of carbohydrate initiators such as sucroseand sorbitol may also be used.

In the process of making a polyisocyanate-based foam, the polyol(s),polyisocyanate and other components are contacted, thoroughly mixed andpermitted to expand and cure into a cellular polymer. The particularmixing apparatus is not critical, and various types of mixing head andspray apparatus are conveniently used. It is often convenient, but notnecessary, to preblend certain of the raw materials prior to reactingthe polyisocyanate and active hydrogen-containing components. Forexample, it is often useful to blend the polyol(s), blowing agent,surfactant(s), catalyst(s) and other components except forpolyisocyanates, and then contact this mixture with the polyisocyanate.Alternatively, all the components may be introduced individually to themixing zone where the polyisocyanate and polyol(s) are contacted. It isalso possible to pre-react all or a portion of the polyol(s) with thepolyisocyanate to form a prepolymer.

The quantity of blowing agent composition employed when preparing a foamis sufficient to give a desired density to the foam. Advantageously,sufficient blowing agent is employed to provide a polyurethane foamhaving an overall density of from about 10 to about 500, preferably fromabout 18 to about 100 kg/m³ (1 kg/m³=0.062 lb./ft.³).

It is often convenient to preblend the blowing agent composition withthe active hydrogen-containing compound before contacting the resultingblend with the polyisocyanate. It is also possible to simultaneouslyblend together the polyisocyanate, active hydrogen-containing compoundand blowing agent composition in one operation resulting in theproduction of polyisocyanate-based foam. Preferably the blowing agentcomposition is blended with the active hydrogen-containing compoundbefore contacting with the polyisocyanate.

One aspect is for a rigid, closed-celled polyisocyanate-based foam. Itis prepared by contacting an organic polyisocyanate with an activehydrogen-containing compound in the presence of the blowing agentcomposition characterized in that the so-prepared foam contains withinits cells gaseous blowing agents.

The rigid closed-cell celled polyisocyanate-based foams are useful inspray insulation, as foam-in-place appliance foams, rigid insulatingboard stock, or in laminates.

In addition, according to certain embodiments, the blowing agents areused to blow thermoplastic foams, such as polystyrene, polyethylenefoams, including low-density polyethylene foams, or polypropylene foams.Any of a wide range of conventional methods for blowing suchthermoplastic foams can be adapted for use herein.

Another embodiment provides a foamable composition comprisingthermoplastic foams, such as polystyrene, polyethylene (PE), preferablylow density PE, or polypropylene (PP).

The thermoplastic foam bodies are conveniently produced by usingconventional equipment comprising an extruder and associated means for(1) melting the resin; (2) homogeneously blending the blowing agentcomposition with the melt to form a plasticized mass at nonfoamingtemperatures and pressures; (3) passing the plasticized mass at acontrolled rate, temperature and pressure through a die having a desiredshape, e.g., slit die for producing rectangular slabs of foam boardhaving desired thickness and surface area, into an expansion zone; (4)allowing the extrudate to foam in the expansion zone maintainable atsuitable temperatures and low pressures; (5) maintaining the expandingextrudate under such temperatures and pressures for a time sufficientfor the viscosity of the extrudate to increase such that the cell sizeand density of the foam remain substantially unchanged and substantiallyfree of ruptured cells at ambient temperature; e.g., 25° C. andatmospheric pressure; and (6) recovering the extruded foam body.

When preparing foams, it is often desirable to add a nucleating agent orother additives into the resin. Nucleating agents serve primarily toincrease cell count and decrease cell size in the foam, and may be usedin an amount of about 0.1 to about 10 parts by weight per 100 parts byweight of the resin. Typical nucleating agents comprise at lease onemember selected from the group consisting of talc, sodiumbicarbonate-citric acid mixtures, calcium silicate, carbon dioxide,among others.

In one aspect, the foaming amount of the blowing agent is in the rangeof from about 1 to about 30 weight percent based on the total weight ofthe resin plus blowing agent mixture, typically about 2 to 20 weightpercent, and normally about 2 to about 10 weight percent. The lower theconcentration of blowing agent, the greater the density of the resultingfoam. The proper amount of blowing agent or resultant characteristics ofthe foam for any desired end-use is readily determined by a skilledperson in this art. The resin is melted at a temperature of about 200 toabout 235° C. depending upon the grade employed, and at nonfoamingpressures of about 600 psig or higher. The plasticized resin-blowingagent mixture is cooled under nonfoaming pressure to a temperature ofabout 115 to 150° C., normally 130° C., and extruded into the expansionzone at or below ambient temperature and at or below atmosphericpressure.

Representative foamed products that can be made in accordance with thepresent disclosure include, for example: (1) polystyrene foam sheet forthe production of disposable thermoformed packaging materials; e.g., asdisclosed in York, U.S. Pat. No. 5,204,169; (2) extruded polystyrenefoam boards for use as residential and industrial sheathing and roofingmaterials, which may be from about 0.5 to 6 inches (1.25 to 15 cm)thick, up to 4 feet (122 cm) wide, with cross-sectional areas of from0.17 to 3 square feet (0.016 to 0.28 square meter), and up to 27 feet(813 meters) long, with densities of from about 1.5 to 10 pounds percubic foot (pcf) (25 to 160 kilograms per cubic meter (kg/m³); (3)expandable foams in the form of large billets which may be up to about 2feet (61 cm) thick, often at least 1.5 feet 46 cm) thick, up to 4 feet(1.22 meters) wide, up to 16 feet (4.8 meters) long, having across-sectional area of about 2 to 8 square feet (0.19 to 0.74 squaremeter) and a density of from 6 to 15 pcf (96 to 240 kg/m³). Such foamedproducts are more fully described by Stockdopole and Welsh in theEncyclopedia of Polymer Science and Engineering, vol. 16, pages 193-205,John Wiley & Sons, 1989; hereby incorporated by reference.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods of this disclosure havebeen described in terms of preferred embodiments, it will be apparent tothose of skill in the art that variations may be applied to thecompositions and methods and in the steps or in the sequence of steps ofthe method described herein without departing from the concept, spirit,and scope of the present disclosure. More specifically, it will beapparent that certain agents which are chemically related may besubstituted for the agents described herein while the same or similarresults would be achieved. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope, and concept of the present disclosure asdefined by the appended claims.

EXAMPLES

The present disclosure is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments, are given by way of illustration only. From the abovediscussion and these Examples, one skilled in the art can ascertain thepreferred features, and without departing from the spirit and scopethereof, can make various changes and modifications to adapt it tovarious uses and conditions.

Example 1 Synthesis of 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene(F14E) Synthesis of C₄F₉CH₂CHICF₃

Perfluoro-n-butyliodide (180.1 gm, 0.52 moles) and3,3,3-trifluoropropene (25.0 gm, 0.26 moles) were added to a 400 mlHastelloy™ shaker tube and heated to 200° C. for 8 hours underautogenous pressure, which increased to a maximum of 428 PSI. Theproduct was collected at room temperature. The above reaction wascarried out again at these conditions and the products combined. It wasthen repeated doubling the amount of perfluoro-n-butyliodide and3,3,3-trifluoropropene in the same 400 ml reactor. In this case thepressure increased to 573 PSI. The products of the three reactions werecombined and distilled to give 322.4 gm of C₄F₉CH₂CHICF₃ (52.2°/35 mm)in 70% yield.

Conversion of C₄F₉CH₂CHICF₃ to F14E

C₄F₉CH₂CHICF₃ (322.4 gm, 0.73 moles) was added dropwise via additionfunnel to a 2 L round bottom flask equipped with stir a bar andconnected to a packed distillation column and still head. The flaskcontained isopropyl alcohol (95 ml), KOH (303.7 gm, 0.54 moles) andwater (303 ml). Product was collected, washed with sodium metabisulfite,water, dried with MgSO₄ and distilled through a 6″ column filled withglass helices. The product, F14E (173.4 gm, 76%) boils at 78.2° C. Itwas characterized by ¹⁹F NMR (δ −66.7 (CF₃, m, 3F), −81.7 (CF₃, m 3F),−124.8 (CF₂, m, 2F), −126.4 (CF₂, m, 2F), and −114.9 ppm (CF₂, m, 2F))¹H NMR (δ 6.4{tilde over (5)}) in chloroform-d solution.

Example 2 Synthesis of1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene (F24E) Synthesis ofC₄F₉CHICH₂C₂F₅

Perfluoroethyliodide (220 gm, 0.895 mole) and3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene (123 gm, 0.50 mole) were added toa 400 ml Hastelloy™ shaker tube and heated to 200° C. for 10 hours underautogenous pressure. The product from this and two others carried outunder similar conditions were combined and washed with two 200 mLportions of 10 wt % aqueous sodium bisulfite. The organic phase wasdried over calcium chloride and then distilled to give 277.4 gm ofC₄F₉CH₂CHICF₃ (79-81° C./67-68 mm Hg) in 37% yield.

Conversion of C₄F₉CHICH₂C₂F₅ to F24E

A 1 L round bottom flask equipped with a mechanical stirrer, additionfunnel, condenser, and thermocouple was charged with C₄F₉CHICH₂C₂F₅(277.4 gm, 0.56 moles) and isopropanol (217.8 g). The addition funnelwas charged with a solution of potassium hydroxide (74.5 g, 1.13 moles)dissolved in 83.8 g of water. The KOH solution was added dropwise to theflask with rapid stirring over the course of about one hour as thetemperature slowly increased from 21° C. to 42° C. The reaction mass wasdiluted with water and the product recovered by phase separation. Theproduct was washed with 50 mL portions of 10 wt % aqueous sodiumbisulfite and water, dried over calcium chloride, and then distilled atatmospheric pressure. The product, F24E (128.7 gm, 63%) boils at 95.5°C. It was characterized by ¹⁹F NMR (δ 81.6 (CF₃, m, 3F), −85.4 (CF₃, m3F), −114.7 (CF₂, m, 2F), −118.1 (CF₂, m, 2F), −124.8 ppm (CF₂, m, 2F),−126.3 ppm (CF₂, m, 2F)) and ¹H NMR (66.48) in chloroform-d solution.

Example 3 Synthesis of CF₃CH═CHCF(CF₃)₂ Synthesis of CF₃CHICH₂CF(CF₃)₂

(CF₃)₂CFI (265 gm, 0.9 moles) and 3,3,3-trifluoropropene (44.0 gm, 0.45moles) were added to a 400 ml Hastelloy shaker tube and heated to 200°C. for 8 hours under autogenous pressure, which increased to a maximumof 585 psi. The product was collected at room temperature to give 110 gmof (CF₃)₂CFCH₂CHICF₃ (76-77° C./200 mm) in 62% yield.

Conversion of (CF₃)₂CFCH₂CHICF₃ to F131E

(CF₃)₂CFCH₂CHICF₃ (109 gm, 0.28 moles) was slowly added dropwise viaaddition funnel to a 500 ml round bottom flask heated to 42° C. equippedwith stir a bar and connected to a short path distillation column anddry ice trap. The flask contained isopropyl alcohol (50 ml), KOH (109gm, 1.96 moles) and water (109 ml). During the addition, the temperatureincreased from 42 to 55° C. After refluxing for 30 minutes, thetemperature in the flask increased to 62° C. Product was collected,washed with water, dried with MgSO₄ and distilled. The product, F131E(41 gm, 55%), boils at 48-50° C. and was characterized by ¹⁹F NMR (δ−187.6 (CF, m 1F), −77.1 (CF3, m 6F), −66.3 (CF3, m 3F) in chloroform-dsolution.

Polyisocyanate-Based Foam Examples

To demonstrate effectiveness of unsaturated fluorocarbon blowing agents,polyurethane and polyisocyanurate foam samples were prepared byhand-mixing, using the two basic polyurethane foam formulationsdescribed in Example 4 and Example 5 below. The blowing agents may begenerally premixed with the polyol or B-side for convenience. Foams maybe prepared either as free-rise or molded samples. For free-rise foams,the reaction mixture is poured into an open, round cardboard container.For molded foams, the reaction mixture is poured into a 2½″×13″×15″(6.35 cm×30.02 cm×38.1 cm) heated aluminum mold.

Example 4 Polyisocyanurate Foam

Component Parts by Weight aromatic polyester polyol (Stepanpol ® 120PS-2502A) polysiloxane surfactant (Dabco DC- 1.8 193) potassiumoctanoate catalyst 3.2 (Hexcem 977) Tris-2,4,6- 0.4(dimethylaminomethyl)phenol/Bis(di- methylaminomethyl)phenol catalyst(Dabco TMR 30) 1,1,1,4,4,5,5,5,Octafluooro-2-pentene 80 (HFC-1438mzz)(Blowing Agent) polymethylene polyphenylisocyanate 190 isocyanate(Papi ® 580)

All components except the isocyanate were premixed as a B-side. Theisocyanate (A-side) was then added and mixed with a mechanical stirrerfor 10 seconds. The foam reaction mixture was poured into a closedaluminum mold warmed to about 100° F. and allowed to expand. When cured,a 1″×1″×12″ sample was cut from the core of the molded foam.

The core sample was about 2.2 pounds/ft³ (PCF) (35.2 kg/m³) density, hadan exceptionally fine cell structure, and remained dimensionally stable.Magnified photographs of the foam showed a uniform, highly closed cellstructure and cell sizes about 200-300 microns (μ). Using a LaserCompFOX 304 Thermal Conductivity Meter, initial insulation value (R-value)was measured at 7.4/inch (thermal conductivity of 19.5 milliW/(mK) at amean temperature of 24.0° C. or 0.135 BTU-in/hr-ft²-° F. at a meantemperature of 75.2° F.).

Example 5 Polyurethane Pour-in-Place Foam

Component Parts by Weight sucrose/glycerine initiated polyether 140polyol (Voranol ® 360) silicone surfactant (Witco L-6900) 3.0N,N-Dimethylcyclohexylamine 1.7 catalyst (Polycat 8)pentamethyldiethylenetriamine 0.4 catalyst (Polycat 5) 2-Methyl(n-methylamino b-sodium 0.5 acetate nonyl phenol) catalyst (Curithane ® 52) Water2.1 Blowing Agent 70 1,1,1,4,4,5,5,5,Octafluooro-2-pentene (HFC-1438mzz)polymethylene polyphenylisocyanate 169 isocyanate (Papi ® 27)

All components except the isocyanate were premixed as a B-side. Theisocyanate (A-side) was then added and mixed with a mechanical stirrerfor 10 seconds. The foam reaction mixture was poured into a closedaluminum mold warmed to about 100° F. and allowed to expand. When cured,a 1″×1″×12″ sample was cut from the core of the molded foam.

The core sample was about 2.0 pounds/ft³ (PCF) (32.0 kg/m³) density, hada good cell structure though it did contain some voids, and remaineddimensionally stable. Magnified photographs of the foam showed auniform, highly closed cell structure, excluding the voids, and cellsizes about 200-300 microns (μ). Using a LaserComp FOX 304 ThermalConductivity Meter, initial insulation value was measured at 4.9/inch(29.5 milliW/(mK) at a mean temperature of 24.0° C. or thermalconductivity of 0.2044 BTU-in/hr-ft²-° F. at a mean temperature of 75.2°F.),

Example 6 Polyisocyanurate Foam

Component Parts by Weight aromatic polyester polyol 14.4 (Stepanpol ®PS-2502A) polysiloxane surfactant 0.42 (Dabco DC-193) Potassiumoctanoate catalyst 0.8 (Hexcem 977)Tris-2,4,6-(dimethylaminomethyl)phenol/Bis(di- 0.15methylaminomethyl)phenol catalyst (Dabco TMR 30) 1,1,1,4,4,4Hexafluooro-2-butene 12.0 (HFC-1336mzz, Z-isomer) (Blowing Agent)polymethylene polyphenylisocyanate isocyanate 22.8 (Papi ® 580)

All components except the isocyanate were premixed as a B-side. Theisocyanate (A-side) was then added and hand-mixed for about 30 seconds.The foam reaction mixture was allowed to rise in the beaker. The blowingagent mixed well with the B-side and foamed the polymer. Foam densitywas initially high because the catalyst amounts and ratio were notoptimal for the HFC-1336mzz boiling point, and the amounts of catalystwere adjusted to decrease density.

Example 7 Blowing Agent Solubility Effect on Foam Cell Structure

These unsaturated fluorocarbons offer an advantage of improved foam cellstructure because their solubility is different than other typicallyused blowing agents. Their reduced solubility in the B-side requiresproper mixing, but once mixed, they demonstrate a good affinity for theB-side, and being somewhat insoluble, act to help seed small cell growthduring the foaming reaction.

This was observed in preparing the foam examples 4 and 5, above. In thecase of example 4, the blowing agent (HFC-1438mzz) was mixed in theB-side until a mousse-like consistency was obtained. At that point, theblowing agent was well dispersed in the B-side, with no loss uponsitting at room temperature. When this B-side mixture was foamed, itresulted in the exceptionally fine cell structure described above, andcontributed to the high R-value.

In example 5, the blowing agent was not mixed as thoroughly in theB-side. In this case, voids were observed in the foam, but the cellstructure excluding the voids remained small and consistent. Theresultant insulation value was acceptable despite the voids,demonstrating that these unsaturated fluorocarbons can improve cellstructure and foam properties such as to overcome potential processingdifficulties that otherwise would detrimentally impact foam performance.

Thermoplastic Foam Examples Example 8

The following example serves to illustrate the ability to useunsaturated fluorocarbon blowing agents to produce thermoplastic foaminsulation, specifically a polystyrene insulation foam, with fine,uniform cell structure, long-term insulation value, and good dimensionalstability.

To produce polystyrene foam insulation board, a commercial tandemextruder equipped with die, designed for insulation board foam, is used.Such a configuration employs a primary extruder and a secondaryextruder, with a slit die. A typical polystyrene resin would be ShellNX600 general purpose, 2.5 melt index, and a typical nucleator would bemagnesium silicate talc.

TABLE 4 Typical Extruder Operating Parameters Primary extruder (rpm) 70Extrusion rate (kg/hr) 430 Blowing agent rate (kg/hr) 46.5 Blowing agentconcentration (wt %) 10.8 Nucleator concentration (wt %) 0.6 Secondaryextruder speed (rpm) 4.9 Die pressure (psig) 1484 Melt temperature (°C.) 129 Die gap (mm) 1.9 Die width (mm) 100 Foam thickness (mm) 52 Foamwidth (mm) 317 Foam density (kg/m³) 30.5

Example 9

In this example, polystyrene foam sheet is prepared using unsaturatedfluorocarbons as the blowing agent. The polystyrene foam sheet isultimately thermoformed into food service packaging, like egg cartons,hamburger cartons, meat trays, plates, etc.

Foam sheet is produced using a conventional tandem extrusion system.Foam is extruded through an annular die, stretched over a mandrel about4 times the die's diameter, and slit to produce a single sheet.

A typical formulation is:

88 to 97 wt. percent polystyrene resin

2 to 8 wt. percent unsaturated fluorocarbon blowing agent

1 to 4 wt. percent nucleating agent

The polystyrene sheet is typically extruded to a thickness of 50 to 300mils and at a rate of approximately 1,000 pounds of plastic per hour.Typical extruder conditions range from 1,000 to 4,000 psi (70.3 kg/cm to281.3 kg/cm) and 200° F. to 400° F. (93.3° C. to 204.4° C.). The blowingagent concentration in the feed material will change depending on thedesired thickness (thicker product requires more blowing agent). Oncethe polystyrene has been extruded, it is typically aged between 3 daysto 2 weeks. During this time, it is stored in rolls in a warehouse. Someblowing agent permeates out of the foam at this time, but at arelatively slow rate.

After storage, the rolls of foam are thermoformed, producing the desiredtype of end-product (e.g., clam-shell containers, plates, etc.).

Example 10

Experiments were conducted to assess the stability of HFC-1225ye forthermoplastic foams. 1,2,3,3,3-pentafluoro-1-propene (HFC-1225ye),1,1-difluoroethane (HFC-152a) and 1,1,1,2-tetrafluoroethane (HFC-134a)were all analyzed by GC/MS prior to the testing and were found to be100% pure. Polystyrene, talc nucleator, a 1010 Mild Steel Coupon, andair was heated to 260° C. in a pressure vessel with blowing agent andheld 24 hours. After 24 hours, the vessel was cooled and all gaseousproducts were collected from the vessel for analysis.

GC/MS Analysis of Gases after Exposure to 260° C. for 24 Hours SampleNumber 24a 24b 24c 32b 39c 32a 39b 39d 22 24d 39a Composition in Wt %:Polystyrene 90 90 87 87 87 87 87 87 87 87 87 Mistron Vapor  3  3  3  3 3  3 Magnesium Silicate Talc Safoam ® FPN3  3  3  3 (sodium salts ofcarbonic & polycarboxylic acids) HFC-1225ye 10 10 10 10 10 10 10 10HFC-152a 10 10 HFC-134a 10 1010 Mild Steel x x x x x x x x x x X CouponAir X x x x x x x x x x X Blowing Agent >99.9% 93.4% 96.7% 100% >99.9%Purity after Exposure

The test data show that HFC-1225ye was surprisingly as stable asHFC-134a and more stable than HFC-152a under extrusion conditions.

The steel coupons from runs 32a, 32b and 24d were analyzed by ElectronSpectroscopy for Chemical Analysis (ESCA). Fluoride ions (F⁻) wereobserved on the surface of all coupons. Estimated concentrations offluoride ion are shown in the table below.

ESCA Analysis Results (unit: atom %) Fluoride ion Sample Number BlowingAgents Talc (atom %) 32a HFC-152a Mistron 15 32b HFC-1225ye Mistron 0.324d HFC-1225ye Safoam 0.2 39d HFC-1225ye Mistron 0.3

Example 11

Experiments were conducted to assess the compatibility of theunsaturated fluorocarbons for thermoplastic foams. Polystyrene and talcnucleator were heated to 260° C. in a pressure vessel with blowing agentand held 24 hours. After 24 hours, the vessel was cooled and apolystyrene sample recovered for thermal gravimetric analysis (TGA).Weight loss versus temperature was compared for the polystyrene samplesheated with blowing agents to a control sample of starting polystyrenematerial. The TGA analysis shows that blowing agent was admixed in themelt and the weight loss provides an approximation of the amount ofblowing agent that mixed in the melt. The data indicates improvedsolubility for the unsaturated fluorocarbon blowing agent versus currentHFC products.

Weight Loss@ # Sample Blowing Agent 300° C. — Polystyrene Control None 0.7% 24a Polystyrene 1,2,3,3,3-pentafluoro-1- 4.26% propene 24bPolystyrene 1,2,3,3,3-pentafluoro-1-  2.5% propene 39c Polystyrene +Talc 1,2,3,3,3-pentafluoro-1- 5.38% propene 39b Polystyrene + TalcHFC-152a 2.44% 39d Polystyrene + Talc HFC-134a 3.99% 39a Polystyrene +Safoam 1,2,3,3,3-pentafluoro-1- 4.79% propene

We claim:
 1. A method of forming a foam comprising: (a) adding a blowing agent to a foamable composition, said blowing agent comprising at least one fluorocarbon or hydrofluorocarbon selected from the group consisting of: (i) a hydrofluorocarbon having the formula E- or Z—R¹CH═CHR², wherein R¹ and R² are, independently, C₁ to C₆ perfluoroalkyl groups; and (ii) a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF₃CF═CHF, CF₃CH═CF₂, CHF₂CF═CF₂, CHF₂CH═CHF, CF₃CF═CH₂, CF₃CH═CHF, CH₂FCF═CF₂, CHF₂CH═CF₂, CHF₂CF═CHF, CHF₂CF═CH₂, CF₃CH═CH₂, CH₃CF═CF₂, CH₂FCHCF₂, CH₂FCF═CHF, CHF₂CH═CHF, CF₃CF═CFCF₃, CF₃CF₂CF═CF₂, CF₃CF═CHCF₃, CF₃CF₂CF═CH₂, CF₃CH═CHCF₃, CF₃CF₂CH═CH₂, CF₂═CHCF₂CF₃, CF₂═CFCHFCF₃, CF₂═CFCF₂CHF₂, CHF₂CH═CHCF₃, (CF₃)₂C═CHCF₃, CF₃CF═CHCF₂CF₃, CF₃CH═CFCF₂CF₃, (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂, CF₃(CF₂)₃CF═CF₂, CF₃CF₂CF═CFCF₂CF₃, (CF₃)₂C═C(CF₃)₂, (CF₃)₂CFCF═CHCF₃, CF₂═CFCF₂CH₂F, CF₂═CFCHFCHF₂, CH₂═C(CF₃)₂, CH₂CF₂CF═CF₂, CH₂FCF═CFCHF₂, CH₂FCF₂CF═CF₂, CF₂═C(CF₃)(CH₃), CH₂═C(CHF₂)(CF₃), CH₂═CHCF₂CHF₂, CF₂═C(CHF₂)(CH₃), CHF═C(CF₃)(CH₃), CH₂═C(CHF₂)₂, CF₃CF═CFCH₃, CH₃CF═CHCF₃, CF₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CF₃, CF₂═CHCF₂CF₂CF₃, CF₂═CFCF₂CF₂CHF₂, CHF₂CF═CFCF₂CF₃, CF₃CF═CFCF₂CHF₂, CF₃CF═CFCHFCF₃, CHF═CFCF(CF₃)₂, CF₂═CFCH(CF₃)₂, CF₃CH═C(CF₃)₂, CF₂═CHCF(CF₃)₂, CH₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CHF₂, CH₂═C(CF₃)CF₂CF₃, CF₂═CHCH(CF₃)₂, CHF═CHCF(CF₃)₂, CF₂═C(CF₃)CH₂CF₃, CH₂═CFCF₂CF₂CHF₂, CF₂═CHCF₂CH₂CF₃, CF₃CF═C(CF₃)(CH₃), CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂, CH₂FCH═C(CF₃)₂, CH₃CF═C(CF₃)₂, CH₂═CHCF₂CHFCF₃, CH₂C(CF₃)CH₂CF₃, (CF₃)₂C═CHC₂F₅, (CF₃)₂CFCF═CHCF₃, CH₂═CHC(CF₃)₃, (CF₃)₂C═C(CH₃)(CF₃), CH₂═CFCF₂CH(CF₃)₂, CF₃CF═C(CH₃)CF₂CF₃, CF₃CH═CHCH(CF₃)₂, CH₂═CHCF₂CF₂CF₂CHF₂, (CF₃)₂C═CHCF₂CH₃, CH₂═C(CF₃)CH₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅, CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂, CF₃CF═CHCH(CF₃)(CH₃), (CF₃)₂C═CFC₂H5, cyclo-CF₂CF₂CF₂CH═CH—, cyclo-CF₂CF₂CH═CH—, CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃, cyclo-CF₂CF₂CF═CF—, cyclo-CF₂CF═CFCF₂CF₂—, cyclo-CF₂CF═CFCF₂CF₂CF₂, CF₃CF₂CF₂CF₂CH═CH₂, CF₃CH═CHCF₂CF₃, CF₂CF₂CH═CHCF₂CF₃, CF₃CH═CHCF₂CF₂CF₃, CF₃CF═CFC₂F₅, CF₃CF═CFCF₂CF₂C₂F₅, CF₃CF₂CF═CFCF₂C₂F₅, CF₃CH═CFCF₂CF₂C₂F₅, CF₃CF═CHCF₂CF₂C₂F₅, CF₃CF₂CH═CFCF₂C₂F₅, CF₃CF₂CF═CHCF₂C₂F₅, C₂F₅CF₂CF═CHCH₃, C₂F₅CF═CHCH₃, (CF₃)₂C═CHCH₃, CF₃C(CH₃)═CHCF₃, CHF═CFC₂F₅, CHF₂CF═CFCF₃, (CF₃)₂C═CHF, CH₂FCF═CFCF₃, CHF═CHCF₂CF₃, CHF₂CH═CFCF₃, CHF═CFCHFCF₃, CF₃CH═CFCHF₂, CHF═CFCF₂CHF₂, CHF₂CF═CFCHF₂, CH₂CF═CFCF₃, CH₂FCH═CFCF₃, CH₂═CFCHFCF₃, CH₂═CFCF₂CHF₂, CF₃CH═CFCH₂F, CHF═CFCH₂CF₃, CHF═CHCHFCF₃, CHF═CHCF₂CHF₂, CHF₂CF═CHCHF₂, CHF═CFCHFCHF₂, CF₃CF═CHCH₃, CF₂═CHCF₂Br, CHF═CBrCHF₂, CHBr═CHCF₃, CF₃CBr═CFCF₃, CH₂═CBrCF₂CF₃, CHBr═CHCF₂CF₃, CH₂═CHCF₂CF₂Br, CH₂═CHCBrFCF₃, CH₃CBr═CHCF₃, CF₃CBr═CHCH₃, (CF₃)₂C═CHBr, CF₃CF═CBrCF₂CF₃, E-CHF₂CBr═CFC₂F₅, Z—CHF₂CBr═CFC₂F₅, CF₂═CBrCHFC₂F₅, (CF₃)₂CFCBr═CH₂, CHBr═CF(CF₂)₂CHF₂, CH₂═CBrCF₂C₂F₅, CF₂═C(CH₂Br)CF₃, CH₂═C(CBrF₂)CF₃, (CF₃)₂CHCH═CHBr, (CF₃)₂C═CHCH₂Br, CH₂═CHCF(CF₃)CBrF₂, CF₂═CHCF₂CH₂CBrF₂, CFBr═CHCF₃, CFBr═CFCF₃, CF₃CF₂CF₂CBr═CH₂, and CF₃(CF₂)₃CBr═CH₂; and (b) reacting or extruding the foamable composition under conditions effective to form a foam.
 2. The method of claim 1, wherein the blowing agent is selected from (i), and R¹ and R² are, independently, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, or C(CF₃)₂CF₂C₂F₅.
 3. The method of claim 1, wherein the blowing agent blowing agent is selected from (i) and wherein the hydrofluorocarbon is CF₃CH═CHCF₃, CF₃CH═CHC₂F₅, CF₃CH═CHCF₂C₂F₅, CF₃CH═CHCF(CF₃)₂, C₂F₅CH═CHC₂F₅, CF₃CH═CH(CF₂)₃CF₃, CF₃CH═CHCF₂CF(CF₃)₂, CF₃CH═CHCF(CF₃)C₂F₅, CF₃CH═CHC(CF₃)₃, C₂F₅CH═CHCF₂C₂F₅, C₂F₅CH═CHCF(CF₃)₂, CF₃CH═CH(CF₂)₄CF₃, CF₃CH═CHCF₂CF₂CF(CF₃)₂, CF₃CH═CHC(CF₃)₂C₂F₅, C₂F₅CH═CH(CF₂)₃CF₃, C₂F₅CH═CHCF₂CF(CF₃)₂, C₂F₅CH═CHCF(CF₃)C₂F₅, C₂F₅CH═CHC(CF₃)₃, C₂F₅CF₂CH═CHCF₂C₂F₅, (CF₃)₂CFCH═CHCF(CF₃)₂, C₂F₅CH═CHCF(CF₃)₂, CF₃CH═CH(CF₂)₅CF₃, CF₃CH═CHCF(CF₃)(CF₂)₂C₂F₅, CF₃CH═CHC(CF₃)₂CF₂C₂F₅, C₂F₅CH═CH(CF₂)₄CF₃, C₂F₅CH═CHCF₂CF₂CF(CF₃)₂, C₂F₅CH═CHC(CF₃)₂C₂F₅, C₂F₅CF₂CH═CH(CF₂)₃CF₃, C₂F₅CF₂CH═CHCF₂CF(CF₃)₂, C₂F₅CF₂CH═CHCF(CF₃)C₂F₅, C₂F₅CF₂CH═CHC(CF₃)₃, (CF₃)₂CFCH═CH(CF₂)₃CF₃, (CF₃)₂CFCH═CHCF₂CF(CF₃)₂, (CF₃)₂CFCH═CHCF(CF₃)C₂F₅, (CF₃)₂CFCH═CHC(CF₃)₃, C₂F₅CH═CH(CF₂)₅CF₃, C₂F₅CH═CHCF(CF₃)(CF₂)₂C₂F₅, C₂F₅CH═CHC(CF₃)₂CF₂C₂F₅, C₂F₅CF₂CH═CH(CF₂)₄CF₃, C₂F₅CF₂CH═CHCF₂CF₂CF(CF₃)₂, C₂F₅CF₂CH═CHC(CF₃)₂C₂F₅, (CF₃)₂CFCH═CH(CF₂)₄₄CF₃, (CF₃)₂CFCH═CHCF₂CF₂CF(CF₃)₂, (CF₃)₂CFCH═CHC(CF₃)₂C₂F₅, CF₃(CF₂)₃CH═CH(CF₂)₃CF₃, CF₃(CF₂)₃CH═CHCF₂CF(CF₃)₂, CF₃(CF₂)₃CH═CHCF(CF₃)C₂F₅, CF₃ (CF₂)₃CH═CHC(CF₃)₃, (CF₃)₂CFCF₂CH═CHCF₂CF(CF₃)₂, (CF₃)₂CFCF₂CH═CHCF(CF₃)C₂F₅, (CF₃)₂CFCF₂CH═CHC(CF₃)₃, C₂F₅CF(CF₃)CH═CHCF(CF₃)C₂F₅, C₂F₅CF(CF₃)CH═CHC(CF₃)₃, or (CF₃)₃CCH═CHC(CF₃)₃.
 3. The method of claim 1, wherein the foamable composition comprises an isocyanate, at least one polyol, and at least one catalyst.
 4. The method of claim 1, wherein the foamable composition further comprises a resin, wherein said resin is polystyrene, polypropylene or polyethylene.
 5. The method of claim 4, wherein the foamable composition further comprises a nucleating agent.
 6. The method of claim 3, wherein the blowing agent comprises a fluorocarbon selected from the group consisting of E-CF₃CF═CHF, Z—CF₃CF═CHF, E-CF₃CH═CHCF₃, Z—CF₃CH═CHCF₃, E-CF₃CH═CFCF₃, Z—CF₃CH═CFCF₃, E-CF₃CF═CFCF₃, Z—CF₃CF═CFCF₃, E-CF₃CH═CHCF₂CF₃, Z—CF₃CH═CHCF₂CF₃, E-CF₃CF═CHCF₂CF₃, Z—CF₃CF═CHCF₂CF₃, E-CF₃CH═CFCF₂CF₃, Z—CF₃CH═CFCF₂CF₃, E-CF₃CF═CFCF₂CF₃, CF₃CF═CFCF₂CF₃, and Z—CF₃CF═CFCF₂CF₃.
 7. A method of forming a polyisocyanate-based foam comprising reacting at least one organic polyisocyanate with at least one active hydrogen-containing compound in the presence of a blowing agent, said blowing agent comprising at least one fluorocarbon or hydrofluorocarbon selected from the group consisting of: (i) a hydrofluorocarbon having the formula E- or Z—R¹CH═CHR², wherein R¹ and R² are, independently, C₁ to C6 perfluoroalkyl groups; and (ii) a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF₃CF═CHF, CF₃CH═CF₂, CHF₂CF═CF₂, CHF₂CH═CHF, CF₃CF═CH₂, CF₃CH═CHF, CH₂FCF═CF₂, CHF₂CH═CF₂, CHF₂CF═CHF, CHF₂CF═CH₂, CF₃CH═CH₂, CH₃CF═CF₂, CH₂FCHCF₂, CH₂FCF═CHF, CHF₂CH═CHF, CF₃CF═CFCF₃, CF3CF₂CF═CF₂, CF₃CF═CHCF₃, CF₃CF₂CF═CH₂, CF₃CH═CHCF₃, CF₃CF₂CH═CH₂, CF₂═CHCF₂CF₃, CF₂═CFCHFCF₃, CF₂═CFCF₂CHF₂, CHF₂CH═CHCF₃, (CF₃)₂C═CHCF₃, CF₃CF═CHCF₂CF₃, CF₃CH═CFCF₂CF₃, (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂, CF₃(CF₂)₃CF═CF₂, CF₃CF₂CF═CFCF₂CF₃, (CF₃)₂C═C(CF₃)₂, (CF₃)₂CFCF═CHCF₃, CF₂═CFCF₂CH₂F, CF₂═CFCHFCHF₂, CH₂═C(CF₃)₂, CH₂CF₂CF═CF₂, CH₂FCF═CFCHF₂, CH₂FCF₂CF═CF₂, CF₂═C(CF₃)(CH₃), CH₂═C(CHF₂)(CF₃), CH₂═CHCF₂CHF₂, CF₂═C(CHF₂)(CH₃), CHF═C(CF₃)(CH₃), CH₂═C(CHF₂)₂, CF₃CF═CFCH₃, CH₃CF═CHCF₃, CF₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CF₃, CF₂═CHCF₂CF₂CF₃, CF₂═CFCF₂CF₂CHF₂, CHF₂CF═CFCF₂CF₃, CF₃CF═CFCF₂CHF₂, CF₃CF═CFCHFCF₃, CHF═CFCF(CF₃)₂, CF₂═CFCH(CF₃)₂, CF₃CH═C(CF₃)₂, CF₂═CHCF(CF₃)₂, CH₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CHF₂, CH₂═C(CF₃)CF₂CF₃, CF₂═CHCH(CF₃)₂, CHF═CHCF(CF₃)₂, CF₂═C(CF₃)CH₂CF₃, CH₂═CFCF₂CF₂CHF₂, CF₂═CHCF₂CH₂CF₃, CF₃CF═C(CF₃)(CH₃), CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂, CH₂FCH═C(CF₃)₂, CH₃CF═C(CF₃)₂, CH₂═CHCF₂CHFCF₃, CH₂C(CF₃)CH₂CF₃, (CF₃)₂C═CHC₂F₅, (CF₃)₂CFCF═CHCF₃, CH₂═CHC(CF₃)₃, (CF₃)₂C═C(CH₃)(CF₃), CH₂═CFCF₂CH(CF₃)₂, CF₃CF═C(CH₃)CF₂CF₃, CF₃CH═CHCH(CF₃)₂, CH₂═CHCF₂CF₂CF₂CHF₂, (CF₃)₂C═CHCF₂CH₃, CH₂═C(CF₃)CH₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅, CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂, CF₃CF═CHCH(CF₃)(CH₃), (CF₃)₂C═CFC₂H5, cyclo-CF₂CF₂CF₂CH═CH—, cyclo-CF₂CF₂CH═CH—, CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃, cyclo-CF₂CF₂CF═CF—, cyclo-CF₂CF═CFCF₂CF₂—, cyclo-CF₂CF═CFCF₂CF₂CF₂, CF₃CF₂CF₂CF₂CH═CH₂, CF₃CH═CHCF₂CF₃, CF₂CF₂CH═CHCF₂CF₃, CF₃CH═CHCF₂CF₂CF₃, CF₃CF═CFC₂F₅, CF₃CF═CFCF₂CF₂C₂F₅, CF₃CF₂CF═CFCF₂C₂F₅, CF₃CH═CFCF₂CF₂C₂F₅, CF₃CF═CHCF₂CF₂C₂F₅, CF₃CF₂CH═CFCF₂C₂F₅, CF₃CF₂CF═CHCF₂C₂F₅, C₂F₅CF₂CF═CHCH₃, C₂F₅CF═CHCH₃, (CF₃)₂C═CHCH₃, CF₃C(CH₃)═CHCF₃, CHF═CFC₂F₅, CHF₂CF═CFCF₃, (CF₃)₂C═CHF, CH₂FCF═CFCF₃, CHF═CHCF₂CF₃, CHF₂CH═CFCF₃, CHF═CFCHFCF₃, CF₃CH═CFCHF₂, CHF═CFCF₂CHF₂, CHF₂CF═CFCHF₂, CH₂CF═CFCF₃, CH₂FCH═CFCF₃, CH₂═CFCHFCF₃, CH₂═CFCF₂CHF₂, CF₃CH═CFCH₂F, CHF═CFCH₂CF₃, CHF═CHCHFCF₃, CHF═CHCF₂CHF₂, CHF₂CF═CHCHF₂, CHF═CFCHFCHF₂, CF₃CF═CHCH₃, CF₂═CHCF₂Br, CHF═CBrCHF₂, CHBr═CHCF₃, CF₃CBr═CFCF₃, CH₂═CBrCF₂CF₃, CHBr═CHCF₂CF₃, CH₂═CHCF₂CF₂Br, CH₂═CHCBrFCF₃, CH₃CBr═CHCF₃, CF₃CBr═CHCH₃, (CF₃)₂C═CHBr, CF₃CF═CBrCF₂CF₃, E-CHF₂CBr═CFC₂F₅, Z—CHF₂CBr═CFC₂F₅, CF₂═CBrCHFC₂F₅, (CF₃)₂CFCBr═CH₂, CHBr═CF(CF₂)₂CHF₂, CH₂═CBrCF₂C₂F₅, CF₂═C(CH₂Br)CF₃, CH₂═C(CBrF₂)CF₃, (CF₃)₂CHCH═CHBr, (CF₃)₂C═CHCH₂Br, CH₂═CHCF(CF₃)CBrF₂, CF₂═CHCF₂CH₂CBrF₂, CFBr═CHCF₃, CFBr═CFCF₃, CF₃CF₂CF₂CBr═CH₂, and CF₃(CF₂)₃CBr═CH₂.
 8. The method of claim 7, wherein the at least one active hydrogen-containing compound is preblended with the blowing agent before reacting with at least one polyisocyanate.
 9. The method of claim 7, wherein the at least one active hydrogen-containing compound/blowing agent blend contains at least 5 to 50 wt. % blowing agent, based on the total weight of active hydrogen-containing compound and blowing agent.
 10. The method of claim 9, wherein the at least one active hydrogen-containing compound/blowing agent blend contains at least 5 to 25 wt. % blowing agent, based on the total weight of active hydrogen-containing compound and blowing agent.
 11. A method of producing polyurethane foams, comprising the steps of blending at least one active hydrogen containing compound and at least one blowing agent to form a B side mixture, said blowing agent comprising a hydrofluorocarbons selected from the group consisting of E-CF₃CF═CHF, Z—CF₃CF═CHF, E-CF₃CH═CHCF₃, Z—CF₃CH═CHCF₃, E-CF₃CH═CFCF₃, Z—CF₃CH═CFCF₃, E-CF₃CF═CFCF₃, Z—CF₃CF═CFCF₃, E-CF₃CH═CHCF₂CF₃, Z—CF₃CH═CHCF₂CF₃, E-CF₃CF═CHCF₂CF₃, Z—CF₃CF═CHCF₂CF₃, E-CF₃CH═CFCF₂CF₃, Z—CF₃CH═CFCF₂CF₃, E-CF₃CF═CFCF₂CF₃, and Z—CF₃CF═CFCF₂CF₃, and reacting said B side mixture with an A side mixture, said A side mixture comprising at least one organic polyisocyanate.
 12. The method of claim 11, wherein the at least one organic polyisocyanate, the at least one active hydrogen-containing compound, and the blowing agent of claim 1 are blended simultaneously.
 13. The method of claim 12, wherein the reacting step is performed in the presence of at least one catalyst.
 14. The method of claim 12, wherein the B side further comprises at least one auxiliary component, said auxiliary component selected from the group consisting of a surfactant, a flame retardant, a preservative, a colorant, an antioxidant, a reinforcing agent, a filler, an antistatic agent, or a combination thereof.
 15. The method of claim 14, wherein the at least surfactant is present in a range of from about 0.2 to about 5 parts surfactant per 100 parts by weight polyol.
 16. The method of claim 15, wherein the at least one surfactant is a liquid or solid organosilicone compound, a polyethylene glycol ether of a long chain alcohol, a tertiary amine or alkanolamine salt of a long chain alkyl acid sulfate ester, an alkyl sulfonic ester, or an alkyl arylsulfonic acid.
 17. The method of claim 13, wherein the at least one catalyst is present in a range of from about 0.1 to about 5 parts catalyst per 100 parts by weight of polyol.
 18. A method of making a thermoplastic foam, comprising the steps of forming a melt comprising a foamable composition, wherein said foamable composition is polystyrene, polyethylene, or polypropylene, blending a blowing agent composition with the melt to form a plasticized mass at nonfoaming temperatures and pressures; passing the plasticized mass at a controlled rate, temperature and pressure through a die and into an expansion zone to form an extrudate, allowing the extrudate to foam in the expansion zone, maintaining the expanding extrudate under such temperatures and pressures for a time sufficient for the viscosity of the extrudate to increase such that the cell size and density of the foam remain substantially unchanged and substantially free of ruptured cells at 25° C. and atmospheric pressure, wherein said blowing agent comprises a fluorocarbon, said fluorocarbon selected from the group consisting of (i) a hydrofluorocarbon having the formula E- or Z—R¹CH═CHR², wherein R¹ and R² are, independently, C₁ to C₆ perfluoroalkyl groups; and (ii) a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF₃CF═CHF, CF₃CH═CF₂, CHF₂CF═CF₂, CHF₂CH═CHF, CF₃CF═CH₂, CF₃CH═CHF, CH₂FCF═CF₂, CHF₂CH═CF₂, CHF₂CF═CHF, CHF₂CF═CH₂, CF₃CH═CH₂, CH₃CF═CF₂, CH₂FCHCF₂, CH₂FCF═CHF, CHF₂CH═CHF, CF₃CF═CFCF₃, CF3CF₂CF═CF₂, CF₃CF═CHCF₃, CF₃CF₂CF═CH₂, CF₃CH═CHCF₃, CF₃CF₂CH═CH₂, CF₂═CHCF₂CF₃, CF₂═CFCHFCF₃, CF₂═CFCF₂CHF₂, CHF₂CH═CHCF₃, (CF₃)₂C═CHCF₃, CF₃CF═CHCF₂CF₃, CF₃CH═CFCF₂CF₃, (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂, CF₃(CF₂)₃CF═CF₂, CF₃CF₂CF═CFCF₂CF₃, (CF₃)₂C═C(CF₃)₂, (CF₃)₂CFCF═CHCF₃, CF₂═CFCF₂CH₂F, CF₂═CFCHFCHF₂, CH₂═C(CF₃)₂, CH₂CF₂CF═CF₂, CH₂FCF═CFCHF₂, CH₂FCF₂CF═CF₂, CF₂═C(CF₃)(CH₃), CH₂═C(CHF₂)(CF₃), CH₂═CHCF₂CHF₂, CF₂═C(CHF₂)(CH₃), CHF═C(CF₃)(CH₃), CH₂═C(CHF₂)₂, CF₃CF═CFCH₃, CH₃CF═CHCF₃, CF₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CF₃, CF₂═CHCF₂CF₂CF₃, CF₂═CFCF₂CF₂CHF₂, CHF₂CF═CFCF₂CF₃, CF₃CF═CFCF₂CHF₂, CF₃CF═CFCHFCF₃, CHF═CFCF(CF₃)₂, CF₂═CFCH(CF₃)₂, CF₃CH═C(CF₃)₂, CF₂═CHCF(CF₃)₂, CH₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CHF₂, CH₂═C(CF₃)CF₂CF₃, CF₂═CHCH(CF₃)₂, CHF═CHCF(CF₃)₂, CF₂═C(CF₃)CH₂CF₃, CH₂═CFCF₂CF₂CHF₂, CF₂═CHCF₂CH₂CF₃, CF₃CF═C(CF₃)(CH₃), CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂, CH₂FCH═C(CF₃)₂, CH₃CF═C(CF₃)₂, CH₂═CHCF₂CHFCF₃, CH₂C(CF₃)CH₂CF₃, (CF₃)₂C═CHC₂F₅, (CF3)₂CFCF═CHCF₃, CH₂═CHC(CF₃)₃, (CF₃)₂C═C(CH₃)(CF₃), CH₂═CFCF₂CH(CF₃)₂, CF₃CF═C(CH₃)CF₂CF₃, CF₃CH═CHCH(CF₃)₂, CH₂═CHCF₂CF₂CF₂CHF₂, (CF₃)₂C═CHCF₂CH₃, CH₂═C(CF₃)CH₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅, CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂, CF₃CF═CHCH(CF₃)(CH₃), (CF₃)₂C═CFC₂H5, cyclo-CF₂CF₂CF₂CH═CH—, cyclo-CF₂CF₂CH═CH—, CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃, cyclo-CF₂CF₂CF═CF—, cyclo-CF₂CF═CFCF₂CF₂—, cyclo-CF₂CF═CFCF₂CF₂CF₂, CF₃CF₂CF₂CF₂CH═CH₂, CF₃CH═CHCF₂CF₃, CF₂CF₂CH═CHCF₂CF₃, CF₃CH═CHCF₂CF₂CF₃, CF₃CF═CFC₂F₅, CF₃CF═CFCF₂CF₂C₂F₅, CF₃CF₂CF═CFCF₂C₂F₅, CF₃CH═CFCF₂CF₂C₂F₅, CF₃CF═CHCF₂CF₂C₂F₅, CF₃CF₂CH═CFCF₂C₂F₅, CF₃CF₂CF═CHCF₂C₂F₅, C₂F₅CF₂CF═CHCH₃, C₂F₅CF═CHCH₃, (CF₃)₂C═CHCH₃, CF₃C(CH₃)═CHCF₃, CHF═CFC₂F₅, CHF₂CF═CFCF₃, (CF₃)₂C═CHF, CH₂FCF═CFCF₃, CHF═CHCF₂CF₃, CHF₂CH═CFCF₃, CHF═CFCHFCF₃, CF₃CH═CFCHF₂, CHF═CFCF₂CHF₂, CHF₂CF═CFCHF₂, CH₂CF═CFCF₃, CH₂FCH═CFCF₃, CH₂═CFCHFCF₃, CH₂═CFCF₂CHF₂, CF₃CH═CFCH₂F, CHF═CFCH₂CF₃, CHF═CHCHFCF₃, CHF═CHCF₂CHF₂, CHF₂CF═CHCHF₂, CHF═CFCHFCHF₂, CF₃CF═CHCH₃, CF₂═CHCF₂Br, CHF═CBrCHF₂, CHBr═CHCF₃, CF₃CBr═CFCF₃, CH₂═CBrCF₂CF₃, CHBr═CHCF₂CF₃, CH₂═CHCF₂CF₂Br, CH₂═CHCBrFCF₃, CH₃CBr═CHCF₃, CF₃CBr═CHCH₃, (CF₃)₂C═CHBr, CF₃CF═CBrCF₂CF₃, E-CHF₂CBr═CFC₂F₅, Z—CHF₂CBr═CFC₂F₅, CF₂═CBrCHFC₂F₅, (CF₃)₂CFCBr═CH₂, CHBr═CF(CF₂)₂CHF₂, CH₂═CBrCF₂C₂F₅, CF₂═C(CH₂Br)CF₃, CH₂═C(CBrF₂)CF₃, (CF₃)₂CHCH═CHBr, (CF₃)₂C═CHCH₂Br, CH₂═CHCF(CF₃)CBrF₂, CF₂═CHCF₂CH₂CBrF₂, CFBr═CHCF₃, CFBr═CFCF₃, CF₃CF₂CF₂CBr═CH₂, and CF₃(CF₂)₃CBr═CH₂.
 19. The method of claim 18, wherein the blowing agent is E-CF₃CF═CHF, Z—CF₃CF═CHF, E-CF₃CH═CHCF₃, Z—CF₃CH═CHCF₃, E-CF₃CH═CFCF₃, Z—CF₃CH═CFCF₃, E-CF₃CF═CFCF₃, Z—CF₃CF═CFCF₃, E-CF₃CH═CHCF₂CF₃, Z—CF₃CH═CHCF₂CF₃, E-CF₃CF═CHCF₂CF₃, Z—CF₃CF═CHCF₂CF₃, E-CF₃CH═CFCF₂CF₃, Z—CF₃CH═CFCF₂CF₃, E-CF₃CF═CFCF₂CF₃, CF3CF2CF═CH2 or Z—CF₃CF═CFCF₂CF₃.
 20. The method of claim 18, wherein the foamable composition further comprises a nucleating agent.
 21. The method of claim 18, wherein the plasticized mass comprises 88 to 97 wt. percent polystyrene resin 2 to 8 wt. percent blowing agent and 1 to 4 wt. percent nucleating agent.
 22. The method of claim 18, where in the blowing agent is a hydrofluoroolefin having the formula E- or Z—R¹CH═CHR², wherein R¹ and R² are wherein R¹ and R² are, independently, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃, CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅, CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, or C(CF₃)₂CF₂C₂F₅.
 23. The method of claim 18, wherein the plasticized mass comprises 88 to 97 wt. percent polypropylene resin 2 to 8 wt. percent blowing agent and 1 to 4 wt. percent nucleating agent.
 24. The method of claim 18, wherein the plasticized mass comprises 88 to 97 wt. percent polyethylene resin 2 to 8 5 wt. percent blowing agent and 1 to 4 wt. percent nucleating agent.
 25. A method for lowering the GWP of the methods for manufacturing open, closed and multi-modal foams, said method comprising combining at least one fluoroolefin of the present invention with a resin to produce a foamable composition with a GWP (calculated as a weighted average of the GWP for each component of the foamable composition) of less than
 25. 26. A method for lowering the GWP of the methods for manufacturing open, closed and multi-modal foams, said method comprising combining at least one fluoroolefin of the present invention into a B-side mixture to produce a foamable composition with a GWP calculated as a weighted average of the GWP for each component of the foamable composition of less than
 25. 